CN102226256A - Preparation method of Fe66Co10Mo4P4C4B4Si3 block soft-magnetic nanocrystalline/amorphous composite material - Google Patents

Preparation method of Fe66Co10Mo4P4C4B4Si3 block soft-magnetic nanocrystalline/amorphous composite material Download PDF

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CN102226256A
CN102226256A CN 201110155726 CN201110155726A CN102226256A CN 102226256 A CN102226256 A CN 102226256A CN 201110155726 CN201110155726 CN 201110155726 CN 201110155726 A CN201110155726 A CN 201110155726A CN 102226256 A CN102226256 A CN 102226256A
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amorphous
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李福山
邹小珂
张军恒
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Zhengzhou University
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Abstract

The invention relates to a preparation method of a Fe66Co10Mo4P4C4B4Si3 block soft-magnetic nanocrystalline/amorphous composite material, comprising the following steps: annealing a Fe66Co10Mo4P4C4B4Si3 block amorphous alloy in vacuum at a first crystallization peak temperature Tp and preserving heat for a specific time, after annealing, putting the annealed alloy in a cooling medium to fast cool to room temperature. According to the invention, nanocrystallization of the Fe base block amorphous alloy can be realized, and the soft magnetic property can be improved obviously. The method provides a novel technological process of the Fe66Co10Mo4P4C4B4Si3 block soft-magnetic nanocrystalline/amorphous composite material.

Description

Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite
Technical field
The present invention is specifically related to field of metallurgy, relates in particular to a kind of Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite gold.The Fe matrix body soft magnetism that makes thus is nanocrystalline/and amorphous composite has the soft magnetic performance excellent more than its corresponding Fe base block amorphous alloy.
Background technology
Fe base nanometer crystal/amorphous composite has the advantage of high magnetic saturation intensity, low-coercivity, high magnetic permeability and low magnetic hysteresis loss, have the soft magnetic performance more excellent more, have broad application prospects at the power electronics industrial circle than permalloy, siliconized plate, non-crystaline amorphous metal.
Late 1980s, discoveries such as Yoshizawa are to add proper C u in the alloy at Fe-Si-B, and can obtain to be embedded with on amorphous substrate the matrix material of nano-scale α-Fe after suitable subsequent annealing art breading.Because the exchange-coupling interaction of α-Fe phase and amorphous phase makes the alloy of this composition have excellent soft magnetic performance.The main alloy system of existing amorphous nanocrystalline soft magnetic material has Fe-Si-Nb-B-Cu system, Fe-Zr-B-Cu system and Fe-Co-Nb-B-Cu system etc., because the inrichment of Cu, in the process of rapid solidification, can become the core of crystallization forming core, thereby reduced the amorphous formation ability of these alloy systems, be difficult for preparing larger-size block amorphous alloy, only can prepare the thin ribbon shaped sample.Thin band material has three main drawbacks as magneticsubstance: the too thin iron core that causes of band twines number of plies increase, there is a large amount of air between layer and the layer, this causes the iron core density to descend, then certainly will cause the reduction of magneticflux-density: have annealing embrittlement and stress sensitive simultaneously, cause the preparation difficulty of iron core, thereby limited the application of nano crystal soft magnetic material.
In order to obtain the nano amorphous alloy of three-dimensional blocks of large, at first must prepare nano amorphous powder, adopt mechanical alloying method with powder sintered compacting then, make the nano amorphous alloy of block shape.Because in the sintering process of nano material, nanocrystal grow up and the process of densification is two processes of vying each other, therefore obtain the tiny nano-structure of crystal grain in order to guarantee, must have influence on the powder density of block.The block density that the reason nanoparticle is compacted in the actual production process is not high, has a large amount of holes in the body, causes the block magneticsubstance of powder metallurgic method preparation to be difficult to show the excellent magnetism energy.
Pressure crystallization method, at first to the amorphous alloy pressurization, then to the bulk amorphous alloys heating, insulation, naturally cooling, last unloading pressure obtains nanocrystalline/amorphous composite.This method complicated operating process, flow process is many, apparatus expensive.And the block amorphous alloy of preparing is nonmagnetic Zr base block amorphous alloy.
Ultrasonic method can realize bulk amorphous alloys nano-crystallization method, under ultrasound condition, block amorphous alloy is carried out heat treated and realize nano-crystallization, though can realize the nano-crystallization of block amorphous alloy, but used equipment complexity and treatment time be length (30～90min), increased processing cost, and the bulk amorphous alloys of handling do not have soft magnetic performance.
Fe 74Al 4Ga 2P 12B 4Si 4Base block amorphous alloy nano-crystallization method improves soft magnetic performance, though handle by subsequent annealing, has obtained the α-Fe phase of nano-scale, however Fe 74Al 4Ga 2P 12B 4Si 4Block amorphous alloy essence does not belong to soft magnetic materials, and nano-crystallization is handled the back coercive force and is reduced to 94.16Oe=7496A/m.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite, and it realizes Fe by the method for subsequent annealing 66Co 10Mo 4P 4C 4B 4Si 3The nanometer of block amorphous alloy, and then prepare structural compactness height, the soft magnetic performance Fe excellent more than its corresponding Fe base block amorphous alloy 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/amorphous composite.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Bulk nano-crystalline/amorphous composite with the acquisition of block amorphous alloy direct crystallization has the soft magnetic performance excellence mainly may further comprise the steps:
(1) prepares Fe with copper mold casting method with soft magnetic performance 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy;
(2) Fe to preparing 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy carries out dsc analysis, determines the crystallization peak temperature T of this alloy p
(3) utilize silica tube with above-mentioned Fe 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy is sealed up for safekeeping in vacuum system, and makes its vacuum tightness reach 10 -3～10 -5MPa;
(4) high temperature resistance furnace is warming up to crystallization peak temperature T p, treat that furnace temperature will be through the Fe of Vacuum Package of last step after constant 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy is put into resistance furnace, because the silica tube size is less, it is put into resistance furnace moment and just reaches furnace temperature, so its influence to furnace temperature can ignore, and thinks that isothermal annealing handles.Treat to pick up counting after silica tube is put into resistance furnace, after annealing finished in 10 minutes.
(5) annealing is taken out sample after finishing in resistance furnace, and in the water coolant under the room temperature of quenching rapidly, is quickly cooled to room temperature, gets Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/amorphous composite.
Described heat-eliminating medium be water, oil, in any one.
The present invention has actively useful effect:
1. the prepared Fe that goes out 66Co 10Mo 4P 4C 4B 4Si 3Bulk nano-crystalline/amorphous composite is obtained by the direct nano-crystallization of block amorphous alloy, thereby the alloy structure density nanometer powder sintered compact method obtains the density of nano block only up to 70%～80% up to 100%(), soft magnetic performance is excellent more than its corresponding Fe base block amorphous alloy: coercive force obviously reduces; Magnetic permeability improves greatly.
2. in the present invention with Fe 66Co 10Mo 4P 4C 4B 4Si 3Block amorphous alloy is at the first crystallization peak temperature T pComparatively high temps direct crystallization anneal, and then prepare the Fe of soft magnetic performance excellence 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/amorphous composite; This material is obtained by the block amorphous alloy crystallization, and the crystallization condition by the control bulk amorphous alloys can obtain having that structure is tight, defective is less, the composition nanocrystalline or amorphous/nanocrystalline matrix material of bulk accurately; Compare with other technology, technology of the present invention has processing ease, equipment is simple, treating processes is short, low power consumption and other advantages, and the material softer magnetic property that uses this technology to obtain simultaneously is excellent more.
Description of drawings
Fig. 1 is Fe 66Co 10Mo 4P 4C 4B 4Si 3The DSC curve of block amorphous alloy;
Fig. 2 is Fe 66Co 10Mo 4P 4C 4B 4Si 3XRD curve contrast before and after the block amorphous alloy anneal 10min;
Fig. 3 is Fe 66Co 10Mo 4P 4C 4B 4Si 3Magnetic hysteresis loop contrast before and after the block amorphous alloy anneal 10min;
Fig. 4 is Fe 66Co 10Mo 4P 4C 4B 4Si 3XRD curve contrast before and after the block amorphous alloy anneal 5min;
Fig. 5 is Fe 66Co 10Mo 4P 4C 4B 4Si 3Magnetic hysteresis loop contrast before and after the block amorphous alloy anneal 5min.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Related non-crystaline amorphous metal preparation and relevant detection method if no special instructions, are ordinary method among the following embodiment.Used testing installation and reagent among the following embodiment if no special instructions, is commercially available.
1 one kinds of Fe of embodiment 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite gold, may further comprise the steps:
(1) design mix is Fe 66Co 10Mo 4P 4C 4B 4Si 3The Fe base block amorphous alloy, with purity is that pure metal and master alloy more than 99.9% is proportioning raw materials, utilize the mode melt back of arc melting to obtain the uniform mother alloy of composition, utilize the mode of induction melting to melt mother alloy once more, utilize the method for copper mold casting to make the block amorphous alloy of diameter again for 2mm.
(2) to gained Fe of last step 66Co 10Mo 4P 4C 4B 4Si 3Amorphous sample carries out dsc analysis, referring to Fig. 1, obtains the crystallization peak temperature T of this composition alloy pBe 522 ℃, sample was 10 minutes this temperature vacuum annealing treatment times.
(3) high temperature resistance furnace is warming up to 522 ℃, and treats after the homo(io)thermism, will use the Fe of silica tube vacuum preservation 66Co 10Mo 4P 4C 4B 4Si 3Sample is put into vacuum oven isothermal anneal.
(4) when sample after 522 ℃ of insulations finished in 10 minutes, sample is quenched rapidly in the water under the room temperature, realize cooling fast, obtain the block nanometer non-crystaline amorphous metal.
(5) sample after the anneal is carried out XRD analysis (referring to Fig. 2) and magnetic property magnetic hysteresis loop analysis (referring to Fig. 3), relevant magnetic property index sees Table 1.
The magnetic property of 10 minutes front and back of table 1 annealing relatively
Magnetic parameter Coercivity H (A/m) Initial Effective permeability
Figure 2011101557269100002DEST_PATH_IMAGE001
Before the annealing 15.96 1885
After subsequent annealing is handled 1.428 19877
2 one kinds of Fe of embodiment 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite gold, may further comprise the steps:
(1) design mix is Fe 66Co 10Mo 4P 4C 4B 4Si 3The Fe base block amorphous alloy, with purity is that pure metal and master alloy more than 99.9% is proportioning raw materials, utilize the mode melt back of arc melting to obtain the uniform mother alloy of composition, utilize the mode of induction melting to melt mother alloy once more, utilize the method for copper mold casting to make the block amorphous alloy of diameter again for 2mm.
(2) amorphous sample is carried out dsc analysis (with embodiment 1), obtain the crystallization peak temperature T of this composition alloy pIt is 522 ℃.Sample was 5 minutes this temperature vacuum annealing treatment times.
(3) high temperature resistance furnace is warming up to 522 ℃, and treats after the homo(io)thermism, will use the Fe of silica tube vacuum preservation 66Co 10Mo 4P 4C 4B 4Si 3Sample is put into vacuum oven isothermal anneal.
(4) when sample after 522 ℃ of insulations finished in 5 minutes, sample is quenched rapidly in the entry, realize cooling fast, obtain the block nanometer non-crystaline amorphous metal.
(5) sample after the anneal is carried out XRD analysis (referring to Fig. 4) and magnetic property magnetic hysteresis loop analysis (referring to Fig. 5), relevant magnetic property index sees Table 2.
Sample after the anneal is carried out XRD analysis and the analysis of magnetic property magnetic hysteresis loop.
The magnetic property of 5 minutes front and back of table 2 annealing relatively
Magnetic parameter Coercivity H (A/m) Initial Effective permeability
Figure 62553DEST_PATH_IMAGE001
Before the annealing 15.96 1885
After subsequent annealing is handled 3.214 11129
Change each the concrete parameter in the foregoing description, can form a plurality of specific embodiments, be common variation range of the present invention, describe in detail no longer one by one at this.

Claims (2)

1. Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite, may further comprise the steps:
(1) prepares Fe with copper mold casting method with soft magnetic performance 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy;
(2) Fe to preparing 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy carries out dsc analysis, determines the crystallization peak temperature T of this alloy p
(3) utilize silica tube with above-mentioned Fe 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy is sealed up for safekeeping in vacuum system, and makes its vacuum tightness reach 10 -3～10 -5MPa;
(4) high temperature resistance furnace is warming up to crystallization peak temperature T p, treat that furnace temperature will be through the Fe of Vacuum Package of last step after constant 66Co 10Mo 4P 4C 4B 4Si 3Base block amorphous alloy is put into resistance furnace, treats to pick up counting after silica tube is put into resistance furnace, and after annealing finished in 5～20 minutes;
(5) annealing is taken out sample after finishing in resistance furnace, and in the water coolant under the room temperature of quenching rapidly, is quickly cooled to room temperature, gets Fe 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/amorphous composite.
2. Fe according to claim 1 66Co 10Mo 4P 4C 4B 4Si 3The block soft magnetism is nanocrystalline/preparation method of amorphous composite, it is characterized in that described heat-eliminating medium is any one in water, the oil.
CN 201110155726 2011-06-10 2011-06-10 Preparation method of Fe66Co10Mo4P4C4B4Si3 block soft-magnetic nanocrystalline/amorphous composite material Expired - Fee Related CN102226256B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965597A (en) * 2012-10-30 2013-03-13 中国科学院宁波材料技术与工程研究所 Fe-based soft magnetic amorphous alloy with high corrosion resistance and preparation method thereof
CN103692705A (en) * 2013-12-16 2014-04-02 杨全民 Composite magnetic material and preparation method and use thereof
CN103882347A (en) * 2014-03-05 2014-06-25 清华大学 Blocky and stripped ferrum-based amorphous alloy with high magnetic element content, and preparation method
CN103981466A (en) * 2014-05-19 2014-08-13 辽宁科技大学 High-corrosion-resistance iron-based amorphous alloy material and preparation method thereof
CN105755356A (en) * 2016-03-15 2016-07-13 梁梅芹 Preparation method of iron-based nanocrystalline soft magnetic alloy
CN113174547A (en) * 2021-04-30 2021-07-27 郑州大学 Iron-based amorphous alloy powder, preparation method thereof and application thereof in laser cladding
CN113667801A (en) * 2020-07-28 2021-11-19 山东大学 Heat treatment method of amorphous alloy
CN115198210A (en) * 2021-04-08 2022-10-18 中国科学院金属研究所 Method for driving massive amorphous alloy to quickly recover spring without damage and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《APPLIED PHYSICS LETTERS》 20071204 Fushan Li et al. Excellent soft-magnetic properties of (Fe,Co)-Mo-(P,C,B,Si) bulk glassy alloys with ductile deformation bahavior 第234101-1-3页 1-2 第91卷, *
《甘肃工业大学学报》 20030630 宋 等 Fe基非晶软磁合金的纳米晶化及磁性 第14-17页 1-2 第29卷, 第2期 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965597A (en) * 2012-10-30 2013-03-13 中国科学院宁波材料技术与工程研究所 Fe-based soft magnetic amorphous alloy with high corrosion resistance and preparation method thereof
CN103692705A (en) * 2013-12-16 2014-04-02 杨全民 Composite magnetic material and preparation method and use thereof
CN103692705B (en) * 2013-12-16 2015-06-03 杨全民 Composite magnetic material and preparation method and use thereof
CN103882347A (en) * 2014-03-05 2014-06-25 清华大学 Blocky and stripped ferrum-based amorphous alloy with high magnetic element content, and preparation method
CN103882347B (en) * 2014-03-05 2016-11-16 清华大学 The block of high magnetic element content and ribbon Fe-based amorphous alloy and preparation method
CN103981466B (en) * 2014-05-19 2016-08-31 辽宁科技大学 A kind of high corrosion-resistant iron-base amorphous alloy material
CN103981466A (en) * 2014-05-19 2014-08-13 辽宁科技大学 High-corrosion-resistance iron-based amorphous alloy material and preparation method thereof
CN105755356A (en) * 2016-03-15 2016-07-13 梁梅芹 Preparation method of iron-based nanocrystalline soft magnetic alloy
CN113667801A (en) * 2020-07-28 2021-11-19 山东大学 Heat treatment method of amorphous alloy
CN113667801B (en) * 2020-07-28 2022-05-03 山东大学 Heat treatment method of amorphous alloy
CN115198210A (en) * 2021-04-08 2022-10-18 中国科学院金属研究所 Method for driving massive amorphous alloy to quickly recover spring without damage and application thereof
CN113174547A (en) * 2021-04-30 2021-07-27 郑州大学 Iron-based amorphous alloy powder, preparation method thereof and application thereof in laser cladding
CN113174547B (en) * 2021-04-30 2022-11-04 郑州大学 Iron-based amorphous alloy powder, preparation method thereof and application thereof in laser cladding

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